Ceramics International 45 (2019) 21293–21307

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Oxidation-dominated wear behaviors of carbide-based cermets: A T

comparison between WC-WB-Co and Cr3C2-NiCr coatings
Haibin Wanga,b,**, Xifeng Yana, Hannah Zhangb, Mark Geeb, Chong Zhaoa, Xuemei Liua,
Xiaoyan Songa,*
a
College of Materials Science and Engineering, Key Laboratory of Advanced Functional Materials, Education Ministry of China, Beijing University of Technology, Beijing,
100124, China
b
National Physical Laboratory, Hampton Road, Teddington, TW110LW, United Kingdom

A R T I C LE I N FO A B S T R A C T

Keywords: A WC-40WB-12Co coating has been developed and demonstrated to have comparable oxidation resistance, re-
WB markably enhanced hardness (over 2 times higher) and improved wear resistance (2–4 times higher) than the
Cermet coating widely used Cr3C2-25NiCr coating at elevated temperatures. Wear failure of Cr3C2-NiCr coating was dominated
Oxide layer by severe subsurface cracking due to oxidation and its poor high-temperature mechanical properties. By con-
Hardness
trast, in the WC-WB-Co coating, the thin oxide scale formed on the surface increased lubrication and hindered
High temperature wear resistance
further oxidation. The WC-WB-Co coating provided strong mechanical support for the oxide layer. The coating
thereby achieved an outstanding high-temperature wear performance. Based on detailed comparisons, the wear
mechanisms of these carbide-based cermet coatings at elevated temperatures were proposed.

1. Introduction those prepared using commercially available Cr3C2-NiCr powders.

Thermal sprayed Cr3C2-NiCr coatings are one of the few cermet
coatings that simultaneously possess high oxidation, wear and corro-
sion resistance in both high-temperature and corrosive environments
[1–5]. Cr3C2-NiCr coated steel components can be operated at a tem-
perature of 900 °C [1,3], which is much higher than that of WC-Co
based coatings which have a safe working temperature generally below
450 °C [6]. The inferior high-temperature performances of WC-Co
coatings were mainly due to the rapid oxidation of Co binder at above
200 °C [7] and WC at above 600 °C [8–10]. However, WC-Co coatings
(typically with 12 wt% Co) are still more competitive than the com-
monly used Cr3C2-25 wt%NiCr coating for low-temperature wear ap-
plications. This is partly because of the higher room-temperature
hardness of WC compared to Cr3C2 and the excellent interfacial
bonding between WC and Co among carbide-based cermets [11–13].
Also, dissolution of Cr3C2 grains in molten Ni during thermal spraying
of Cr3C2-NiCr coating may lead to a highly brittle metallic binder, and
lead to relatively low wear resistance of the coating [1,14,15].
Recently, several optimized compositions such as Cr3C2-WC-
NiCoCrMo [6] and Cr3C2-WC-Ni [16] have been developed, and these
coatings show improved high-temperature wear resistance compared to
Prolonged aging can be used to enhance the hardness and sliding wear
resistance of the conventional Cr3C2-NiCr coating [17]. In comparison
with the widely used HVOF (High Velocity Oxy-Fuel) spraying, Cr3C2-
NiCr coatings fabricated by supersonic plasma spraying have lower
friction coefficient and wear rate [18]. Previous work on the wear be-
havior of Cr3C2-NiCr coatings at elevated temperatures have shown that
the wear mechanism is mainly oxidation wear in the early stages fol-
lowed by abrasive wear and adhesive wear [5,6,11,16–18]. More spe-
cifically, the failure of the coatings is mainly related to (i) cracks and
delamination in carbides and in the oxidized area, (ii) formation of
grooves, pores and oxides and (iii) softening of the coating at elevated
temperature.
Despite this progress, the improvement in abrasive wear resistance
of the Cr3C2-NiCr coating remains limited compared to WC-Co coating.
Little attention has been paid to enhance the high-temperature wear
performance of WC-Co coatings. One well-publicized challenge is im-
proving the oxidation resistance of WC-Co composite at elevated tem-
peratures. If this problem is solved, the applications of WC-based
coatings can be expanded to a variety of high-temperature environ-
ments.
Because of this background, the present work develops a new

*
Corresponding author.
**
Corresponding author. College of Materials Science and Engineering, Key Laboratory of Advanced Functional Materials, Education Ministry of China, Beijing
University of Technology, Beijing, 100124, China.
E-mail addresses: whb@bjut.edu.cn (H. Wang), xysong@bjut.edu.cn (X. Song).

https://doi.org/10.1016/j.ceramint.2019.07.113
Received 14 May 2019; Received in revised form 9 July 2019; Accepted 9 July 2019
Available online 10 July 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
H. Wang, et al.
Fig. 1. Surface and cross-sectional SEM images of the thermal spray feedstock powders: (a, b) WC-40WB-12Co powder prepared in the present work, (c, d) com-
mercial Cr3C2-25NiCr powder.
ultrafine-structured WC-WB-Co coating by adding an appropriate
amount of WB in conventional WC-Co. The high-temperature oxidation
and wear behaviors of the fabricated WC-WB-Co coating and a com-
mercial Cr3C2-NiCr coating for comparison were investigated based on
studies of the surface and cross-sectional microstructures of the wear
scars.
2. Experimental
2.1. Fabrication of coating
Commercially available WC (0.8 μm, > 99.9%), Co
(0.8 μm, > 99.9%) and WB (2.2 μm, > 99.9%) powders were used to
prepare the target WC-40WB-12Co coating (wt.%). First, the WB
powder was grinded for 40 h with planetary ball milling. Then the pre-
milled WB powder was mixed with suitable amounts of WC and Co
powders through a further ball milling of 20 h. The ball-to-powder ratio
was set as 3:1 in all milling procedures. The mixed WC-WB-Co powder
was agglomerated by spray-drying and subsequently heat-treated at
1180 °C for 5 h. After a sieving procedure, a spherical WC-WB-Co
feedstock powder with the particle size of 15–45 μm was obtained for
thermal spraying. Meanwhile, a commercial Cr3C2-25 wt%NiCr thermal
spray powder (15–45 μm) was also used to prepare the Cr3C2-NiCr
coating for comparison. High velocity oxy-fuel (HVOF) thermal
spraying process (GTV K2) was used to deposit the powders onto a steel
substrate for fabrication of the coatings. The fuel rate, oxygen rate,
spraying distance and feeding rate of powder were 26 L/h, 900 L/min,
360 mm and 90 g/min, respectively.
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2.2. Characterization
The phase constitution of the feedstock powders and coatings were
examined by X-ray diffraction (XRD) using Cu Kα radiation in a Rigaku
Ultimate IV diffractometer. The morphology and microstructures of
powders and coatings were observed by scanning electron microscopy
(SEM, FEI NanoNova SEM 200 and Zeiss Supra 40) and transmission
electron microscope (TEM, FEI Tecnai G2 F20). Thermogravimetric-
differential thermal analysis (TG-DTA) measurements of the coatings
were performed in static air using a SEIKO TG/DTA 6300 instrument.
Before tests, the coatings were completely removed from the substrates
by mechanically twisting. During the TG-DTA analysis, the specimens
were heated to 800 °C and kept at this temperature for 30 min, and then
was heated until the temperature reached 1000 °C. The temperature
increasing rate was 10 °C/min. The elemental composition of the worn
surface of the coatings after high-temperature wear testing was ana-
lyzed by the X-ray photoelectron spectrometer (XPS, ESCALAB 250Xi).
A Micro Materials NanoXtreme indentation system (Wrexham, UK)
in combination with a Berkovich Sapphire indenter was used for eval-
uating the hardness of the coatings. Indentations were performed with
the maximum load of 100 mN, and 40 μm intervals between indents;
and at least 10 indents at different locations were obtained at room and
high temperature. For high temperature measurement, the system was
left in vacuum (10−4 mbar) overnight to stabilize; and both the in-
denter and sample were heated up to 700 °C, with sample surface
temperature reading of 630 °C from a thermal couple soldered on top of
the sample surface. An indentation test was carried out only until the
thermal drift reached as low as 0.03 nm/s, and the result was analyzed
with the standard Olive & Pharr method. Besides, the Vickers hardness
measurements on cross-section of the coatings with a load of 300 g were
carried out using a Future-Tech FM-700 microhardness tester. A ZD-
H. Wang, et al.
Fig. 2. Phase constitutions of the thermal spray powders and as-sprayed coat-
ings: (a) WC-WB-Co, (b) Cr3C2-NiCr.
HVZHT-30 Vickers hardness tester was used to examine the surface
hardness of the coatings under a load of 500 g at room temperature and
800 °C, respectively.
2.3. Wear tests
The room-temperature wear tests were carried out using a re-
ciprocating ball-on-disk tribometer (Lanzhou Zhongke Kaihua
Technology Development Co., Ltd., China). Si3N4 balls with a diameter
of 5 mm were used as the counterpart material. Before tests, all speci-
mens were polished with a final step of 1.5 μm diamond polishing paste
for 30 min. The applied load on the specimens was 80 N. The sliding
speed of the ball was 0.083 m/s and the total sliding time was 30 min.
The high-temperature wear resistance of the coatings was evaluated
using a rotary ball-on-disk tribometer (Anton Paar, Sweden) at 800 °C
for 200 min and 500 min. The counterpart material is Al2O3 ball with a
diameter of 6 mm. The applied load on the coating was 20 N. The linear
velocity was 1.34 m/s and the wear scar radius was 8.5 mm for each
specimen.
The volume loss of the specimens was estimated from the cross-
sectional profiles of the wear scar. Three repeat tests were performed
for each coating. The friction coefficient as a function of sliding time
was recorded automatically during the tests.
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3. Results
3.1. Microstructure of powders and coatings
The surface and cross-sectional microstructures of the WC-40WB-
12Co and Cr3C2-25NiCr thermal spray feedstock powders are shown in
Fig. 1. Both powders have a nearly spherical shape for ensuring a high
flowability during HVOF spraying process. Based on the analysis of the
cross-sectional microstructures and phase constitution (as shown in
Fig. 2) of the feedstock particles, the composition of the marked areas
can be determined, as shown in Fig. 1(b) and (d). The WC-WB-Co
powder consists of WC, WCoB and a small amount of Co3W9C4. The
WCoB phase was formed by the reaction between WB and Co in the
heat-treatment process of feedstock powder [19]. The formation of
Co3W9C4 may be related to slight oxidation of WB, which led to for-
mation of W and the subsequent reactions of W, WC and Co binder in
the heat-treatment process. The commercial Cr3C2-NiCr powder is
composed of Cr3C2 and Ni(Cr) solid solution binder with face-centered
cubic (FCC) structure. Most of the WC particles are in the size range of
0.2–0.3 μm and the sizes of Cr3C2 particles are between 2 and 5 μm.
The phase constitutions of as-sprayed coatings are shown in Fig. 2. It
is found that WCoB and Co3W9C4 in the WC-WB-Co feedstock powder
have transformed into W2CoB2 and Co7W6 in the fabricated coating.
This indicates that slight oxidation occurred during HVOF spraying of
the powder, which caused a loss of carbon in the coating. By contrast,
the phase constitution of the Cr3C2-NiCr coating almost remains the
same as that of the initial powder.
The cross-sectional microstructures of the coatings are shown in
Fig. 3. Both coatings have a very high density. The WC-WB-Co coating
shows a typical lamellar structure; this is not obvious in the Cr3C2-NiCr
coating. This may be because the melting and spreading of WC-WB-Co
particles were not as sufficient as those of Cr3C2-NiCr particles. In both
coatings, the carbides particles distribute homogeneously in the me-
tallic binders.
3.2. Hardness and wear resistance of coatings
The hardness of the coatings measured under various conditions is
listed in Table 1. As shown, the mean room-temperature (RT) hardness
of WC-WB-Co coating is about 30% higher than that of Cr3C2-NiCr
coating no matter whether the measurement is performed on surface or
cross section. At elevated temperatures, both nanoindentation and
Vickers hardness of the WC-WB-Co coating are over 2 times higher than
those of Cr3C2-NiCr coating. It is noted that the temperature rise from
room temperature to 630 °C has led to a 61% decrease in na-
noindentation hardness of Cr3C2-NiCr coating. However, the reduction
is only 32% for the WC-WB-Co coating under the same testing condi-
tions. The above results demonstrate that the prepared WC-WB-Co
coating can maintain a significantly higher mechanical strength than
conventional Cr3C2-NiCr coatings.
The kinetic friction coefficients of both coatings versus sliding dis-
tance at different testing temperatures are shown in Fig. 4. At room
temperature, the friction coefficients of both coatings remain nearly the
same and the mean values are about 0.48. At 800 °C, the mean friction
coefficients of both coatings decrease to 0.35. However, the variation of
friction coefficient of the Cr3C2-NiCr coating is obviously higher than
that of WC-WB-Co coating. This is because severe adhesive wear oc-
curred during the sliding process of Cr3C2-NiCr coating, which will be
discussed later.
The wear rates of both coatings measured at room and elevated
temperatures are shown in Fig. 5. In comparison with Cr3C2-NiCr
coating, the WC-WB-Co coating has significantly enhanced wear re-
sistance under both testing conditions. The wear rate of WC-WB-Co
coating at room temperature is about 1/10 of that of Cr3C2-NiCr
coating. At 800 °C for 200 min, the wear rate of WC-WB-Co coating is
still half of that of Cr3C2-NiCr coating. When the sliding time extends to
H. Wang, et al. Ceramics International 45 (2019) 21293–21307

Fig. 3. Cross-sectional microstructures of the coatings: (a, b) WC-WB-Co, (c, d) Cr3C2-NiCr.

Table 1
Hardness of the coatings measured at room and elevated temperatures.
Method Test position Load (N) Temperature Cr3C2-NiCr (Ha) WC-WB-Co (Hb) (Hb-Ha)/Ha (%)

Vickers hardness (GPa) Cross section 3 RT 10.70 ± 0.71 13.93 ± 1.28 30

Surface 5 RT 8.34 ± 0.03 10.99 ± 1.39 32
Surface 5 800 °C 4.65 ± 0.04 10.00 ± 1.06 119
Nanoindentation hardness (GPa) Cross section 0.1 RT 14.00 ± 4.80 18.26 ± 2.52 31
Cross section 0.1 630 °C 5.41 ± 1.64 12.39 ± 2.31 130

500 min, the wear rate of WC-WB-Co coating is almost not changed.
However, the mean wear rate of Cr3C2-NiCr coating has increased by 2
times compared to that measured for 200 min. In other words, the high-
temperature wear resistance of WC-WB-Co coating is improved by 2–4
times relative to conventional Cr3C2-NiCr coatings.
difference between the mass increase rates of the coatings should be
slightly larger. Based on the theoretical contents of carbides in the
coatings, the mass increase rates caused by oxidation of WC and Cr3C2
are estimated to be 8.8% and 20.0%, respectively. This means that more
WC must have been oxidized to reach the higher mass increase rate of
the WC-WB-Co coating in comparison with Cr3C2-NiCr coating.

3.3. Oxidation resistance of the coatings WC + 2O2 = WO3 + CO↑ (1)

2WC + 5O2 = 2WO3 + 2CO2 ↑ (2)

The oxidation resistance of the coatings was evaluated by TG-DTA
thermal analyses, as shown in Fig. 6. For both DTA curves, there is a
broad exothermic peak, which should result from the oxidation reac-
tions of various constituents of the coatings. The exothermic rates
achieved their maximum at about 512 °C and 553 °C for WC-WB-Co
coating and Cr3C2-NiCr coating, respectively. During the isothermal
heating process at 800 °C, the WC-WB-Co coating shows a mass increase
rate of 0.56% while it is only 0.29% for Cr3C2-NiCr coating. At the end
of the tests, the total mass increase rates of the coatings are very low,
indicating that both coatings have an excellent oxidation resistance
below 1000 °C. However, the total mass increase rate of WC-WB-Co
coating (i.e. 4.3%) is higher than that of Cr3C2-NiCr coating (i.e. 1.3%).
Moreover, if the release of carbon oxides caused by the oxidation of
carbides (as described by Reactions (1)-(4)) was taken into account, the
4Cr3C2 + 13O2 = 6Cr2O3 + 8CO↑ (3)
4Cr3C2 + 17O2 = 6Cr2O3 + 8CO2 ↑ (4)
The phase constitutions of the coatings after wear tests at 800 °C for
500 min are shown in Fig. 7. Severe oxidation occurred on both surfaces
of the coatings during the wear process. A large amount of CoWO4 and
WO3 phases can be observed in the WC-WB-Co coating. The main phase
of Cr3C2-NiCr coating is Cr23C6 which should result from the oxidation
of Cr3C2 and Cr3O2 is also detected.
3.4. Surface observation of the wear scar
The surface morphology and corresponding element distribution on

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Fig. 4. Kinetic friction coefficients of the coatings versus sliding distance at

different testing temperatures: (a) 25 °C, (b) 800 °C.

Fig. 6. TG-DTA thermal analysis of the coatings in static air: (a) WC-WB-Co
coating, (b) Cr3C2-NiCr coating.

Fig. 5. Wear rate of the coatings measured at room temperature and 800 °C.

the wear scar of Cr3C2-NiCr coating after wear test at 800 °C for 200 min Fig. 7. XRD patterns of the coatings after wear testing at 800 °C for 500 min.
are shown in Fig. 8. There are many cracks occurring in the unworn
surface (on the left side) of this coating. The cracks may be formed due
adhesive wear of Cr3C2-NiCr coating may result from the interactions
to the oxidation-induced volume expansion of coating material. The
between Ni and the mating Al2O3 ball.
wear scar (see Fig. 8(b)) is partially covered with Al and O, as evi-
Furthermore, XPS measurements were carried out to investigate the
denced by the corresponding element mapping images. The elements Al
chemical bonding state of surface elements on the wear scar. The XPS
and O should come from the mating Al2O3 ball, indicating the occur-
spectra of the Cr3C2-NiCr coating are shown in Fig. 9. The full range
rence of adhesive wear between the Cr3C2-NiCr coating and the coun-
survey XPS spectrum (see Fig. 9(a)) shows the presence of C 1s, O 1s, Cr
terpart material during high-temperature wear process. Moreover, it is
2p, Ni 2p and Al 2p levels. As shown in Fig. 9(b), the high-resolution Cr
detected that the amount of Cr in the O-rich area (probably Cr2O3) is
2p and Ni 2p spectra confirm that the Cr and Ni elements on the wear
obviously higher than that in the Al-rich zone. However, Ni distributes
scar exist in the form of Cr3O2 and NiO, respectively. The high-re-
homogeneously in the whole observed area. This suggests that the
solution O 1s XPS spectra (Fig. 9(d)) can be curve-fitted into three peaks

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Fig. 8. SEM micrographs of wear scar of the Cr3C2-NiCr coating after wear testing at 800 °C and corresponding EDS element mapping images for Cr, Ni, Al and O of
the region of (b).
with a binding energy of 533.67 eV, 531.69 eV and 529.71 eV, which
corresponds to Al2O3, Cr3O2 and NiO, respectively [20–23].
The microstructure images of the Cr3C2-NiCr coating after wear
testing at 800 °C for 500 min are shown in Fig. 10. The wear failure of
this coating is thought to occur as a result of the following sequence of
events: (i) formation of nanoscale Cr3O2 and NiO particles due to the
oxidation of coating (see Fig. 10(d)); (ii) fracture, delamination and
peeling-off of oxide scales in localized regions (see Fig. 10(a), (b) and
(c)); (iii) detachment of certain oxide layers that were metallurgically
bonded to the mating Al2O3 ball. It appears that the wear rate depends
largely on the characteristics and mechanical properties of the oxide
scales.
Fig. 11 shows the surface morphology and corresponding element
distribution on wear scar of the WC-WB-Co coating. Unlike the Cr3C2-
NiCr coating, the severe cracking morphology is not observed in the
unworn surface (see the left side of Fig. 11(a)) of WC-WB-Co coating.
The EDS mapping spectrum (Fig. 11(b)) shows that there are mainly W,
Co and O in the wear scar and Al is not detected. These elements are
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evenly distributed within the observed area (Fig. 11(c)). The high-
magnification image of the unworn surface of WC-WB-Co coating and
corresponding element distribution are shown in Fig. 12. Certain parts
of the coating were protruded out of the top surface. As determined by
EDS mapping analysis, these areas contain much more Co and O than
other areas. This confirms that the protrusions on the unworn area of
WC-WB-Co coating are possibly Co-containing oxides (i.e. CoWO4).
XPS spectra of WC-WB-Co coating after high-temperature wear
testing are shown in Fig. 13. The wide range survey spectrum
(Fig. 13(a)) shows the presence of C 1s, O 1s, B 1s, Co 2p, Co 3p, W 4p,
W 4d and W 4f levels. The W 4f7/2 peak at 35.52 eV (Fig. 14(b)) in
combination with the Co 2p3/2 peak at 781.34 eV (Fig. 13(c)) confirms
the formation of WO3 and CoWO4 [24]. The high-resolution B 1s
spectrum with the binding energy of 192.19 eV coincides well with that
of B2O3 [25], indicating the formation of B2O3 phase during the wear
process though it is not detected by XRD analysis. In addition, the high-
resolution O 1s spectrum fitted with three peaks at 533.21 eV,
531.56 eV and 530.49 eV further proves the formation of B2O3, CoWO4
H. Wang, et al. Ceramics International 45 (2019) 21293–21307

Fig. 9. XPS spectra of the Cr3C2-NiCr coating after wear testing at 800 °C: (a) full spectrum, (b) Cr, (c) Ni and (d) O.

Fig. 10. SEM micrographs of the Cr3C2-NiCr coating at different magnifications after wear testing at 800 °C for 500 min.

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Fig. 11. SEM micrographs of wear scar of the WC-WB-Co coating after wear testing at 800 °C and corresponding EDS element mapping images for O, Co and W of the
region of (c).

and WO3, respectively.
The microstructure images of WC-WB-Co coating after wear testing
at 800 °C for 500 min and the unworn surface for comparison are shown
in Fig. 14. From the low-magnification images (Fig. 14(a) and (b)), it is
found that there are not any cracks in the wear scar. The WC-WB-Co
coating has a relatively flat surface. This indicates that the coating and
its surface oxide layer as a whole did not undergo significant plastic
deformation. However, there is evidence of ploughing occurred in the
oxide layer of WC-WB-Co coating, as shown in Fig. 14(b). This suggests
that plastic deformation has occurred in the oxide layer. The depth of
the wear trace is very shallow because of the extremely small thickness
of the oxide layer (which will be shown later). In addition, the
occurrence of liquid B2O3 (with a melting point of about 450 °C) during
the high-temperature wear process may increase the viscosity of the
oxide mixture including WO3 and CoWO4. This is also favorable for the
deformation of the oxide layer. During the repeated shear deformation
process of the oxide layer, micro-cracks may initiate at the boundaries
between oxide particles, which eventually leads to the removal of the
particles as shown in Fig. 14(b) and (c). In the unworn area, the oxides
have grown freely into needle-like or hexagonal crystals with obviously
denser microstructure and larger grain sizes compared to those at the
friction area. Evidently, the growth of oxide scale was largely affected
by friction. Two factors may contribute to this result. First, the contact
area between coating and friction counterpart was isolated from

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Fig. 12. SEM micrograph of the unworn area of the WC-WB-Co coating after wear testing at 800 °C and corresponding EDS elemental mapping images for O, Co and
W.
oxygen. Second, the previously formed oxide layers might be damaged
due to friction.
3.5. Cross-sectional microstructure of wear scar
Cross-sectional microstructures of wear scar of both coatings after
wear testing at 800 °C for 200 min are shown in Fig. 15. Several cracks
were initiated beneath the wear scar of Cr3C2-NiCr coating and ex-
tended from surface towards the substrate. The cracks mainly propa-
gated along the Ni-Cr binder containing many fine precipitated grains.
This phenomenon is consistent with that observed on the top surface of
the coating. In contrast, no obvious cracks are observed in the subsur-
face area of WC-WB-Co coating.
To get more understanding, TEM observation of the cross-sectional
microstructures of wear scars was performed for both coatings with the
assistance of focused ion beam technology for the preparation of TEM
film samples. As shown in Fig. 16(a), the thickness of oxide scale of
Cr3C2-NiCr coating is estimated to be approximately 2 μm. Based on the
EDS mapping images and the XPS analysis results (Fig. 9), it is de-
termined that the dark and bright grains in the oxide layer are Cr2O3
and NiO, respectively. The composition of the grey grains is possibly
Al2O3. Interestingly, the Al2O3 particles are mostly distributed in the
NiO matrix. This explains how the Al2O3 layer was formed on the Cr3C2-
NiCr coating. It is possibly caused by the penetration of hard Al2O3
debris into the soft Ni-Cr binder. There is no evidence that a chemical
reaction has occurred between Al2O3 and Ni.
The HAADF-STEM cross-sectional microstructure of the wear scar of
WC-WB-Co coating after wear testing at 800 °C for 200 min and corre-
sponding EDS element mapping images are shown in Fig. 17. The
thickness of oxide scale is estimated to be approximately 1.3 μm. A
high-magnification image of the oxide scale shows that the oxides
mostly have a grain size of about 50 nm, as shown in Fig. 17(b). Fur-
thermore, the high-resolution TEM images of the selected grains con-
firmed the existence of CoWO4 and W3O8, as indicated by the indexing
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in Fig. 18. W3O8 may be an intermediate state between W and WO3.
4. Discussion
It is known that conventional WC-Co coatings are not suitable for
high-temperature applications due to the rapid oxidation of both WC
and Co binder above a critical temperature of about 600 °C [8–10]. How
to solve this problem has been a big concern for researchers and in-
dustries for a long term. Though Cr3C2-NiCr coatings exhibit much
higher oxidation resistance than WC-Co coatings, there is still space for
the improvement of their wear performance at elevated temperatures.
In the present work, the fabricated WC-WB-Co coating has much higher
room- and high-temperature hardness and comparably excellent oxi-
dation resistance compared to Cr3C2-NiCr coatings, thus exhibiting re-
markably enhanced wear resistance at even 800 °C. In this section, the
factors and mechanisms controlling the high-temperature tribological
properties of these cermet coatings are discussed.
The above results demonstrate that the hardness of the cermet
coatings may decrease a lot at elevated temperatures besides the severe
oxidation. Particularly, the metal matrix has decreased ability to resist
against the penetration of abrasives and wear debris. As a result, plastic
deformation and ploughing wear could be more serious with the in-
crease of temperature. In addition, an oxide layer generally formed on
the cermet coatings. There may be chemical reactions and atomic dif-
fusion between coating and wear counterpart, leading to a transfer of
materials. Accordingly, the thickness, mechanical strength and che-
mical stability of the oxide scale, and the high-temperature hardness
and fracture toughness of coating are possibly the factors influencing
the high-temperature wear performance of the cermet coatings.
As the constituents of coating have poor oxidation resistance, the
oxide scale grows fast. During the high-temperature wear process, the
wear performance of coating is largely dependent on the mechanical
properties of the thick oxide layer. The conventional WC-Co coatings
can be taken as an example, as illustrated in Fig. 19(a). At high
H. Wang, et al.
Fig. 13. XPS spectra of the WC-WB-Co coating after wear testing at 800 °C: (a) full spectrum, (b) W, (c) Co, (c) B and (d) O.
temperatures, fast oxidation of WC particles and Co binder occurs, re-
sulting in the formation of large amounts of WO3 and CoWO4 with low
load-bearing capacity [26]. The oxide layer can be easily removed by
micro-cutting, leading to the exposure of subsurface layer of coating to
air. In such a way, the conventional WC-Co coatings have relatively
high wear rate at elevated temperatures.
When the constituents of coating have high oxidation resistance, the
oxide scale can be as thin as 1–2 μm. In this case, the high-temperature
properties of the oxides have less influence on the wear performance of
coating. Instead, the oxide particles may act as a lubricant between
coating and mating body. The friction coefficient can thus be reduced.
Meanwhile, a dense oxide scale is capable to protect the subsurface
coating from further oxidation. Moreover, the oxides may have higher
hardness than the un-oxidized metal (e.g. the Cr2O3 film can achieve a
hardness of 18.1 GPa [27] while the hardness of Ni-Cr film is approxi-
mately between 5 and 6 GPa [28]). In this case, the oxide scale is
beneficial to the wear performance of coating. However, the scale of
oxidation is too small to mechanically resist against the compression
and penetration of a hard and sharp asperity. As the supporting body of
the oxides, the un-oxidized coating plays a vital role against friction.
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Ceramics International 45 (2019) 21293–21307
The wear process of Cr3C2-NiCr coating can be taken as an example, as
illustrated in Fig. 19(b). At elevated temperatures, the Cr3C2-NiCr
coating has a low hardness and the surface area can easily get fractured
because of oxidation. These facts lead to the lessening of mechanical
integrity of the Cr3C2-NiCr coating. Therefore, the superficial Cr2O3/
NiO oxide layers are readily removed by micro-cutting. When extending
the wear time from 200 min to 500 min, the subsurface cracking of
Cr3C2-NiCr coating becomes more serious because of the propagation of
surface micro-cracks towards the substrate, leading to an accelerated
mean wear rate. Nonetheless, the excellent oxidation resistance of
Cr3C2-NiCr coating partly counteracts the weakness of mechanical
properties, which enables the coating to maintain a relatively low mean
wear rate compared to the conventional WC-Co coatings.
In the present work, the Co binder in conventional WC-Co coatings
is completely substituted by ternary metal borides with significantly
higher hardness and oxidation resistance. The thickness of the CoWO4
and WO3 oxide scale is only 1.3 μm. Due to the lubricative effect of the
nanoscale oxide particles, the friction coefficient of the WC-WB-Co
coating at 800 °C is obviously reduced compared to that at room tem-
perature. Moreover, the WC-WB-Co coating maintains a relatively high
H. Wang, et al. Ceramics International 45 (2019) 21293–21307

Fig. 14. SEM micrographs of (a–c) the WC-WB-Co coating after wear testing at 800 °C for 500 min and (d) the unworn areas.

Fig. 15. SEM microstructure under wear scars of the coatings after wear testing at 800 °C: (a, b) Cr3C2-NiCr coating, (c, d) WC-WB-Co coating.

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Fig. 16. HAADF-STEM images (a, b) of the cross-section of the Al-rich area on the wear track of the Cr3C2-NiCr coating after wear testing at 800 °C for 200 min and
corresponding EDS element mapping images for Cr, Ni, Al and O of the selected region of (b).

hardness until 800 °C. In fact, as reported in our previous work [19],
brittle fracture easily occurs in local areas of the WC-WB-Co coating
during the room-temperature wear tests. However, in the high-tem-
perature wear process as in the present work, the WC-WB-Co coating
has increased tolerance to surface cracking that may be induced by
mechanical factors and oxidation compared to the Cr3C2-NiCr coating.
This indicates the improvement in plasticity of the WC-WB-Co coating
at elevated temperatures. For these reasons, as illustrated in Fig. 19(c),
the WC-WB-Co coating can provide a strong and durable mechanical
support for the oxide layer which inversely protects the coating un-
derneath from rapid oxidation. Thus, except for slight plastic de-
formation, cracking and peeling of the oxide scale were rarely observed
in the worn WC-WB-Co coating. The pull-out of oxide particles caused
by the frictional shear stress may be the dominant reason that leads to
wear failure of the oxide scale. Based on the above facts, the developed
WC-WB-Co coating achieves an outstanding wear performance at ele-
vated temperature.

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Fig. 17. HAADF-STEM images (a, b) of the cross-section of the wear track of the WC-WB-Co coating after wear testing at 800 °C and corresponding EDS element
mapping images for Cr, Ni, Al and O of the selected region of (b).
5. Conclusions
Based on a comparative study of the microstructure, hardness and
wear behaviors between a newly developed ultrafine-structured WC-
WB-Co coating and the conventional Cr3C2-NiCr coating, the following
conclusions are drawn.
(1) WC-WB-Co coatings exhibit a high oxidation resistance comparable
to the widely used conventional Cr3C2-NiCr coating below 1000 °C
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Ceramics International 45 (2019) 21293–21307
owing to the substitution of Co binder by ternary W-Co-B phases.
(2) The hardness of WC-WB-Co coating is about 30% higher than that
of Cr3C2-NiCr coating at room temperature, and the difference be-
tween them increases to more than 2 times at 630–800 °C.
(3) Both the room- and high-temperature wear resistance of WC-WB-Co
coating are remarkably improved compared to the conventional
Cr3C2-NiCr coating. Particularly at 800 °C, the wear rate of WC-WB-
Co coating is only 1/4 of that of Cr3C2-NiCr coating.
(4) The relatively high wear performance of conventional Cr3C2-NiCr
H. Wang, et al. Ceramics International 45 (2019) 21293–21307

Fig. 18. High resolution TEM images of the oxides at the wear scar of the WC-WB-Co coating and corresponding FFT patterns of the selected grains marked with A
and B.

Fig. 19. Schematic diagram showing the wear mechanisms of conventional WC-Co coating (a), Cr3C2-NiCr coating (b) and the WC-WB-Co coating prepared in the
present work.

coating at elevated temperatures is mainly attributed to its excellent Acknowledgements

oxidation resistance which counteracts the weakness of mechanical
properties.
(5) In comparison with Cr3C2-NiCr coating, the WC-WB-Co coating has
a comparably thin oxide scale that can reduce the friction coeffi-
cient and retard further oxidation of coating, and remarkably im-
proved high-temperature hardness and increased tolerance to sur-
face cracking that can provide a strong and durable mechanical
support for the oxide layer, and hence outstanding high-tempera-
ture wear resistance.
This work was supported by the National Natural Science
Foundation of China (51601004, 51631002 and 51425101) and the
National Key Program of Research and Development of China
(2018YFB0703902). The authors would also like to thank China
Scholarship Council (CSC) for providing the financial support (No.
201806545002).
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